US4071580A - Graft polymers - Google Patents

Graft polymers Download PDF

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US4071580A
US4071580A US05/662,263 US66226376A US4071580A US 4071580 A US4071580 A US 4071580A US 66226376 A US66226376 A US 66226376A US 4071580 A US4071580 A US 4071580A
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ethylene
copolymer
acrylonitrile
vinyl
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Heinrich Alberts
Herbert Bartl
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules

Definitions

  • This invention relates to graft polymers consisting of ethylene homopolymers or copolymers as graft substrate and a mixture of (meth)acrylonitrile, aromatic monovinyl compounds and vinyl chloride as graft monomers, and to a process for their preparation.
  • the inhomogeneity of the resulting graft products is particularly troublesome in cases where the graft substrate and styrene/acrylonitrile copolymers are incompatible with each other.
  • the graft products obtained have properties which make them unsuitable for processing and poor mechanical properties. This applies particularly to the system of polyethylene/styrene-acrylonitrile.
  • This problem can be substantially solved by using 0.01 to 15% by weight, preferably 0.1 to 5% by weight, based on the monomer mixture which is required to be grafted on the substrate, of vinyl chloride as regulator in the grafting reaction.
  • the present invention thus relates to a process for the preparation of graft polymers from ethylene homopolymers or copolymers and olefinically unsaturated monomers in the presence of a radical forming agent in homogeneous or heterogeneous phase, in which mixtures of (meth)acrylonitrile, at least one aromatic vinyl compound and vinyl chloride are polymerised in the presence of ethylene homopolymers or copolymers.
  • ethylene homopolymers polyethylenes which are prepared by known methods of low, medium or high pressure synthesis, which may vary in structure from linear to strongly branched and which have molecular weights, as determined by the method of light scattering, of 5000 or more.
  • Suitable ethylene copolymers include ethylene/vinyl ester copolymers preferably containing 1 to 75 % by weight, in particular 5 to 50 % by weight, of vinyl esters built into the copolymers.
  • the vinyl esters may be organic vinyl esters of aliphatic saturated monocarboxylic acids containing 1 to 18 carbon atoms, which may be halogen substituted, in particular chlorine substituted or aromatic monocarboxylic acids containing 7 to 11 carbon atoms.
  • the following are specific examples: Vinyl formate; vinyl acetate; vinyl propionate; vinyl chloropropionate; vinyl butyrate; vinyl isobutyrate; vinyl caproate; vinyl laurate; vinyl myristate; vinyl stearate and vinyl benzoate; vinyl acetate is preferred.
  • the ethylene/vinyl ester copolymers are prepared by known methods of high or medium pressure synthesis, if desired in solvents such as tertiary butanol.
  • the ethylene/vinyl ester copolymers prepared by the high pressure synthesis method have melt index values of from 0.1 to 100, preferably from 1.0 to 10 and more particularly from 4.5 to 6.
  • the intrinsic viscosities determined in tetralin at 120° C are generally from 0.6 to 1.5.
  • the molecular weights determined by the method of light scattering are preferably from 50,000 to about 1 million.
  • the nonuniformity U defined by the term (Mw/Mn) - 1 (G. V. Schulz, in Z. phys. Chem. (B) 43 (1939), pages 25 to 34) is within the range of from 5 to 20.
  • These copolymers are preferably soluble in hot hydrocarbons and may contain up to 40 % by weight of vinyl esters.
  • the ethylene/vinyl ester copolymers prepared, for example, by the solution polymerisation method and containing, for example, 30 to 75 % by weight of vinyl acetate, preferably 40 to 55 % by weight of vinyl acetate, have melt index values which are in part no longer measurable at 190° C according to DIN 53 735 under a loading of 2.16 kp but may also be greater than 100.
  • the melt index range is preferably below 15, and in particular from 3 to 5.
  • the molecular weights determined by the light scattering method are preferably from 40,000 to 500,000.
  • the nonuniformity U is from 2 to 6.
  • the vinyl esters used may be the organic vinyl esters mentioned above.
  • copolymers are soluble in hydrocarbons and those which have higher vinyl ester contents are also soluble in alcohols and preferably have intrinsic viscosities in toluene at 25° C of from 0.5 to 2.0.
  • Suitable ethylene copolymers also include the copolymers of ethylene with ⁇ , ⁇ -monoolefinically unsaturated carboxylic acids containing 3 to 5 carbon atoms and their derivatives. These copolymers preferably contain from 1 to 80 % by weight, in particular from 1 to 30% by weight, of these carboxylic acid derivatives.
  • the preferred ⁇ , ⁇ -monoolefinically unsaturated carboxylic acids with 3 to 5 carbon atoms are (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, and itaconic acid. (Meth)acrylic acid and maleic acid are particularly preferred.
  • Carboxylic acid derivatives of the above mentioned acids may also be used, in particular their monoesters of diesters with 1 to 8 carbon atoms in the alcohol component or their anhydrides.
  • the graft substrates which yield the best results are ethylene homopolymers and ethylene/vinyl ester copolymers, in particular ethylene/vinyl acetate copolymers.
  • the ethylene/vinyl ester copolymers may be partly or completely hydrolysed if desired.
  • the monomers which may be grafted on the substrates include methacrylonitrile and/or acrylonitrile, aromatic monovinyl compounds such as styrene, nuclear substituted alkyl styrenes containing 1 to 5 carbon atoms in the alkyl group, e.g. 4-methylstyrene, ⁇ -methylstyrene, halogenated styrenes such as 4-chlorostyrene or mixtures thereof, preferably styrene and ⁇ -methylstyrene and vinyl chloride.
  • aromatic monovinyl compounds such as styrene, nuclear substituted alkyl styrenes containing 1 to 5 carbon atoms in the alkyl group, e.g. 4-methylstyrene, ⁇ -methylstyrene, halogenated styrenes such as 4-chlorostyrene or mixtures thereof, preferably styrene and ⁇ -methylstyrene and vinyl
  • the quantity of monomer mixture used for graft polymerisation is preferably from 5 to 95% by weight, for 5 to 95 % by weight of an ethylene homopolymer or copolymer.
  • the monomer mixture used for the grafting reaction may vary widely in its percentage composition of the given components.
  • the monomer mixture consists of the following components:
  • the invention also relates to polymer-containing graft polymers of ethylene homopolymers or copolymers with polymerised units of mixtures of (meth)acrylonitrile, aromatic monovinyl compounds and vinyl chloride.
  • the polymers preferably contain graft polymers of
  • Ii 5 to 95 % by weight, preferably 20 to 89.9 % by weight and in particular 54.9 to 80 % by weight of at least one aromatic monovinyl compound and
  • Iii 0.01 to 15 % by weight, preferably 0.1 to 10 % by weight and in particular 0.1 to 5 % by weight of vinyl chloride,
  • polymer-containing graft polymers of ethylene/vinyl ester copolymers with polymerised units of mixtures of (meth)acrylonitrile, aromatic monovinyl compounds and vinyl chloride are particularly interesting.
  • These polymers preferably contain graft polymers of
  • Ii 5 to 95 % by weight, preferably 20 to 89.9 % by weight and in particular 54.9 to 80 % by weight of at least one aromatic monovinyl compound and
  • Iii 0.01 to 15 % by weight, preferably 0.1 to 10 % by weight and in particular 0.1 to 5 % by weight of vinyl chloride,
  • Ii 5 to 95 % by weight, preferably 20 to 89.9 % by weight and in particular 54.9 to 80 % by weight of at least one aromatic monovinyl compound and
  • Iii 0.01 to 15 % by weight, preferably 0.1 to 10 % by weight and in particular 0.1 to 5 % by weight of vinyl chloride,
  • the monomers are mainly grafted on the graft substrate but minor quantities of homopolymers and/or copolymers of the monomers may also be present.
  • the grafting reaction according to the invention may be carried out by introducing all the monomers and vinyl chloride into the reaction vessel in the presence of the graft substrate and polymerising, but alternatively the monomers or monomer mixtures and vinyl chloride may be added to the graft substrate either continuously or intermittently.
  • the radical forming agent may be added in one portion at the beginning of the reaction or continuously or intermittently before, during or after addition of the monomers. In many cases it is advantageous to use several different radical forming agents in the reaction.
  • the graft substrate should preferably be in a finely divided or dissolved form if very homogeneous graft products are to be obtained but, in principle, the reaction may also be carried out with coarsely granulated polyethylene of the kind which is obtained, for example, from high pressure polymerisation of ethylene.
  • the following solvents may suitably be used: Saturated aliphatic or aromatic hydrocarbons such as ethane, propane, the isomeric butanes, pentanes, hexanes or mixtures thereof, petroleum ethers, light fraction petroleum hydrocarbons and other petroleum hydrocarbon fractions, benzene, toluene, the xylene isomers and other substituted benzene derivatives such as chlorobenzene, halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, trichlorofluoromethane and other chloro-fluorohydrocarbons, trichloroethylene, tetrachloroethylene, difluoroethylene, etc. and low boiling alcohols such as methanol, ethanol, propanol, isopropanol or the isomeric butanols, preferably tert
  • Dissolving of the graft substrates may be carried out at temperatures of from about 20° C to 120° C if fairly high boiling solvents are used or if the substrates are dissolved at elevated pressure.
  • the grafting reaction may also be carried out in heterogeneous phase.
  • the graft substrate may be used in the form of granulates, spherical particles, cylindrical particles, platelets or particles in the form of spirals or other shapes.
  • the graft substrates are preferably in the form of powders or granulates with particles measuring from 1 ⁇ to 3 cm.
  • the graft substrates may be brought into contact with the monomer mixture by spraying, brush coating, dipping or dispersing the substrate in the monomer mixture, the monomers then partly or completely swelling into the substrate.
  • the substrate particles may undergo an increase in volume but retain substantially their original shape.
  • the monomer mixture may be used either undiluted or dissolved in solvents or dispersed in an organic diluent and/or water.
  • the diluents used are similar to the solvents mentioned above which are used for carrying out the grafting reaction in solution. Whether the substrate particles are completely dissolved or merely undergo swelling depends on the quantity and nature of the solvent, the temperature, the pressure and the nature of the graft substrate. Swelling is, of course, accompanied by partial solution of the substrate particles, but the dissolved part of the individual substrate particle substantially remains in the undissolved part of the particle, with the result that the particle retains its original shape in spite of its increase in volume.
  • Swelling of the graft substrates may be carried out at temperatures of up to about 85° C, if desired in the presence of polymerisation catalysts.
  • Graft copolymerisation may be carried out in homogeneous or heterogeneous phase at temperatures within a range of from -20° C to 250° C, preferably from 30° C to 150° C, and at pressures of up to 500 excess atmospheres, preferably at pressures of from normal pressure (1 atmosphere) to 21 atmospheres.
  • the process could also quite well be carried out by first preparing a homogeneous phase of graft substrate, aromatic vinyl compound and vinyl chloride and optionally catalyst and solvent, then dispersing the solution in water and then polymerising, if desired after the addition of catalyst.
  • the graft substrate particles which have been caused to swell by the monomer mixture may be polymerised in the presence of inert or substantially inert gases such as nitrogen or carbon dioxide.
  • the graft substrate which has undergone swelling is preferably present in an organic solvent or in water, or in a heterogeneous or homogeneous mixture of solvent and water.
  • Graft copolymerisation may also be carried out as an emulsion polymerisation.
  • a polyethylene latex or ethylene/vinyl ester copolymer latex having a solid content of from 20 to 55 % by weight, preferably 25 to 45 % by weight is further polymerised to a given degree of conversion with continuous addition of the monomers and vinyl chloride on the one hand and of a water initiator solution which may additionally contain emulsifier on the other hand.
  • emulsion graft polymerisation process may also be carried out continously.
  • Suitable for use as initiators are water-soluble radical-forming agents such as potassium or ammonium peroxy disulphate or redox systems.
  • Suitable emulsifiers include, for example, alkyl sulphates and alkyl sulphonates which have 12 to 24 carbon atoms in the alkyl group, hydrogenated or modified resinic acids such as Dresinate 731® of Hercules and saturated or unsaturated carboxylic acids which are modified with polyethylene oxide or propylene oxide.
  • Biologically degradable emulsifiers are preferably used.
  • the polymerisation catalysts are preferably added to the polymerisation mixture before, during or after the dissolving, swelling or mixing process.
  • the polymerisation catalysts are preferably used in a quantity of from 0.01 to 1.5 % by weight, based on the sum of graft substrate and graft monomers, although much larger quantities may, of course, be used if desired.
  • Per-compounds or azo compounds which give rise to radicals may be used as polymerisation catalysts.
  • the following are given as examples: Benzoyl peroxide, tert.-butyl perpivalate, lauroyl peroxide, tert.-butyl peroctoate, tert.-butyl perbenzoate, ditert.-butyl peroxide, tert.-butyl perisononanate, diisopropylpercarbonate, dicyclohexyl percarbonate, acetyl cyclohexylhexanesulphonyl peroxide, dicumyl peroxide, azo-bis-isobutyric acid nitrile, etc..
  • Benzoyl peroxide, tert.-butyl perpivalate, tert.-butyl peroctoate, dicyclohexylpercarbonate, dicumyl peroxide, azo-bis-isobutyric acid nitrile and ditert.-butyl peroxide are particularly suitable.
  • dispersing agents are necessary for obtaining satisfactory bead polymers.
  • the following are given as examples of dispersing agents: Polyvinyl alcohol and partially saponified polyvinyl acetates, cellulose derivatives and starch derivatives such as methyl cellulose, ethyl cellulose or ethyl hydroxycellulose.
  • Suitable synthetic dispersing agents include styrene/(meth)acrylic acid, styrene/maleic acid anhydride and ethylene/(meth)acrylic acid copolymers; copolymers of (meth)acrylic acid esters and (meth)acrylic acid; polyethylene oxides or ethylene-propylene oxide copolymers and polyesters with hydroxyl numbers between 10 and 250.
  • dispersing agents and emulsifiers it is preferred to use biologically degradable emulsifiers.
  • Inorganic salts for example phosphoric acid derivatives
  • Polymerisation in aqueous suspension is preferably carried out at temperatures of from 40° C to 150° C at about 1 to 25 bar.
  • the aqueous suspension polymerisation process may also be carried out as a reverse emulsion polymerisation (waterin-oil) or initially in the form of a reverse emulsion polymerisation and finally as a suspension polymerisation of styrene and acrylonitrile in water.
  • a solution of the monomers and a radical forming agent (organic phase) is first prepared. Water is then added to the organic phase and a water-in-oil emulsion is produced, preferably with the aid of water-in-oil emulsifiers.
  • the initiators or initiator system may be contained in the water. In the system which is to be polymerised, therefore, the disperse phase is formed by water which may contain part or all of the initiator or initiator system and of the monomers and water-in-oil emulsifier while the remaining monomers or all the monomers form the continuous phase. Copolymerisation may already set in during preparation of the water-in-oil emulsion.
  • the water-in-oil emulsifiers which are used in quantities of from 0.05 to 10 % by weight, preferably 0.5 to 4 % by weight, based on the monomers, may include, for example, graft products of styrene or other vinyl monomers on polyethers of ethylene oxide or styrene copolymers containing ⁇ , ⁇ -unsaturated carboxylic acids or a 1:1 copolymer of methacrylic acid and methyl ,methacrylate.
  • Other water-in-oil emulsifiers are also suitable, for example those described in British Patent Specifications Nos. 928,621; 926,699; 959,131; 964,195; and 1,076,319; German Patent Nos. 1,300,286 and 1,211,655 and Belgian Patent No. 785,091.
  • the proportion by weight of aqueous phase to organic phase when preparing the water-in-oil emulsion (first stage) should preferably be within the range of from 0.2:1 to 1:1 A ratio above or below this range may be used, so long as a water-in-oil emulsion can be formed but the ratio of aqueous phase to organic phase should not exceed 3:1.
  • the vinyl chloride may be added with the solution of monomers or at a later stage but at the latest before phase reversal.
  • the polymerisation temperatures during the first stage are from 30° C to 120° C, preferably from 60° C to 85° C. Polymerisation is preferably continued to a degree of conversion of from 10 % to 60 %.
  • the ratio by weight of aqueous phase to oil phase is preferably from 1:1 to 3:1 and should not be more than 10:1.
  • Preparation of the water-in-oil emulsion may be carried out at temperatures of from 10° C to 90° C.
  • the addition of water and, if indicated, dispersing agents in the second stage is carried out after formation of the water-in-oil emulsion and heating or cooling to the polymerisation temperature of the second stage, which is from 40° C to 180° C, preferably from 75° C to 150° C.
  • Substances which have been found suitable for use as dispersing agents are polyvinyl alcohol, partially saponified polyvinyl acetate and alkyl celluloses such as methyl cellulose, alkyl sulphonates or alkyl sulphates. They are used in quantities of from 0.01 to 3 % by weight, preferably 0.5 to 2 % by weight, based on the quantity of monomers used.
  • One particular advantage of this process lies in the simple method of processing and problem-free drying of the resulting bead polymer, which has a porous structure.
  • the graft reaction according to the invention may also be carried out using known redox systems which may be composed of peracid compounds, such as potassium persulphate, and inorganic or organic reducing agents, for example as described in Methoden der Organischen Chemie, Houben-Weyl, 4th Edition (1961), Volume 14/1, pages 263-297.
  • peracid compounds such as potassium persulphate
  • inorganic or organic reducing agents for example as described in Methoden der Organischen Chemie, Houben-Weyl, 4th Edition (1961), Volume 14/1, pages 263-297.
  • Initiator radicals may also be produced with the aid of ultraviolet irradiation which may be carried out in the presence of peracid compounds with or without sensitizer, X-rays, ⁇ -rays, or accelerated electrons.
  • the usual additives such as molecular weight regulators may also be added to the polymerisation reaction mixtures, and, in the case of suspension polymerisation in organic solvents, special dispersing agents such as ethylene/vinyl acetate copolymers containing 45 to 80 % by weight of vinyl acetate or copolymers of (meth)acrylic acid derivatives may also be added.
  • the process according to the invention may be carried out continously or batchwise.
  • the grafting reaction may be carried out with or without solvent in polymerisation screws and evaporation of the solvent or of the residual monomers from the graft polymerisation mixture may be carried out in evaporation screws, thin layer evaporators or spray driers.
  • Tables 1 and 2 show the results of fractional precipitation of a graft product prepared according to the invention (Example 1) and of a reaction product obtained by conventional methods (Comparison Example 1). The same ethylene/vinyl acetate copolymer was used as graft substrate in both experiments.
  • reaction products which have been prepared without the use of vinyl chloride as graft activator are not only chemically non-uniform but, according to their widely differing solution viscosities, they are also very non-uniform in their structure. This explains the difficulty with which such graft products can be processed thermoplastically and their undesirable inhomogeneity.
  • thermoplastic powders with an average particle size of less than 1000 ⁇ which are excellent for coating purposes for various powder application methods such as whirl sintering, flame spraying and electrostatic spraying, or for rotational casting can be obtained directly by the process.
  • the products obtained according to the invention are eminently suitable for use as coating materials and as material which can be thermoplastically processed. Even graft products with high styrene/acrylonitrile contents can be worked up problem-free in the usual machines used in thermoplastic technology. Owing to their excellent compatibility, the graft polymers are in some cases highly transparent. The mechanical strength properties are excellent, in contrast to those of mixtures of thermoplasts, which, as is well known, are completely incompatible and without mechanical strength.
  • the portions of ungrafted graft substrte were separated from the grafted substrate and ungrafted polymerised monomer units by simple and/or double fractional precipitation.
  • the graft product was dissolved (e.g. in dimethylformamide, benzene or toluene/dimethylformamide mixtures), and then gradually precipitated in the heat, e.g. with n-butanol or methanol.
  • the amount of graft substrate in the graft polymer is obtained from the difference between 100 % and the sum of percentages contents of the grafted monomers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
US05/662,263 1975-03-04 1976-02-27 Graft polymers Expired - Lifetime US4071580A (en)

Applications Claiming Priority (2)

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DE2509403A DE2509403C2 (de) 1975-03-04 1975-03-04 Pfropfpolymerisate
DT2509403 1975-03-04

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US (1) US4071580A (enrdf_load_stackoverflow)
JP (1) JPS51126290A (enrdf_load_stackoverflow)
BE (1) BE839124A (enrdf_load_stackoverflow)
CA (1) CA1088245A (enrdf_load_stackoverflow)
DE (1) DE2509403C2 (enrdf_load_stackoverflow)
FR (1) FR2303032A1 (enrdf_load_stackoverflow)
GB (1) GB1517243A (enrdf_load_stackoverflow)
IT (1) IT1061680B (enrdf_load_stackoverflow)
NL (1) NL7602269A (enrdf_load_stackoverflow)
SE (1) SE7601932L (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4153646A (en) * 1976-12-11 1979-05-08 Bayer Aktiengesellschaft Graft copolymers
US4160739A (en) * 1977-12-05 1979-07-10 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
US4161452A (en) * 1977-01-28 1979-07-17 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
US4357445A (en) * 1980-03-07 1982-11-02 Bayer Aktiengesellschaft Process for the production of cross-linked graft copolymers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3008746A1 (de) * 1980-03-07 1981-09-24 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von pfropfcopolymerisaten
JPS636011A (ja) * 1986-06-25 1988-01-12 Sumitomo Chem Co Ltd 塩化ビニルグラフト・エチレン共重合体の製造方法
EP0317680B1 (en) * 1987-11-26 1992-01-22 Elf Atochem S.A. Vinyl chloride-grafted ethylene copolymer useful as impact modifier and for the production of laminates, and process for producing same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853970A (en) * 1971-09-15 1974-12-10 Diamond Shamrock Corp Vinyl chloride graft polymers and process for preparation thereof
US3855353A (en) * 1972-03-30 1974-12-17 Bayer Ag Graft polymers based on ethylene copolymers
US3856733A (en) * 1970-02-05 1974-12-24 Vinyl Prod Ltd Polymerisation process for grafting vinyl chloride on ethylene-vinyl acetate copolymer
US3901954A (en) * 1972-03-30 1975-08-26 Bayer Ag Graft copolymers
USB465688I5 (enrdf_load_stackoverflow) 1973-05-04 1976-01-27
US3954908A (en) * 1972-04-21 1976-05-04 Showa Denko Kabushiki Kaisha Flame retardant resin composition comprising an acrylonitrile-styrene base terpolymer, a different acrylonitrile-styrene-chlorinated polyethylene terpolymer and antimony trioxide
US3962371A (en) * 1973-12-12 1976-06-08 Bayer Aktiengesellschaft Weather-resistant thermoplasts
US3970718A (en) * 1964-01-24 1976-07-20 Showa Denko Kabushiki Kaisha Method of producing polymer compositions based on chlorinated polyethylene
US3988390A (en) * 1973-05-04 1976-10-26 Bayer Aktiengesellschaft Thermoplastic polycarbonate moulding compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1239670A (enrdf_load_stackoverflow) * 1968-12-17 1971-07-21

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970718A (en) * 1964-01-24 1976-07-20 Showa Denko Kabushiki Kaisha Method of producing polymer compositions based on chlorinated polyethylene
US3856733A (en) * 1970-02-05 1974-12-24 Vinyl Prod Ltd Polymerisation process for grafting vinyl chloride on ethylene-vinyl acetate copolymer
US3853970A (en) * 1971-09-15 1974-12-10 Diamond Shamrock Corp Vinyl chloride graft polymers and process for preparation thereof
US3855353A (en) * 1972-03-30 1974-12-17 Bayer Ag Graft polymers based on ethylene copolymers
US3901954A (en) * 1972-03-30 1975-08-26 Bayer Ag Graft copolymers
US3954908A (en) * 1972-04-21 1976-05-04 Showa Denko Kabushiki Kaisha Flame retardant resin composition comprising an acrylonitrile-styrene base terpolymer, a different acrylonitrile-styrene-chlorinated polyethylene terpolymer and antimony trioxide
USB465688I5 (enrdf_load_stackoverflow) 1973-05-04 1976-01-27
US3988390A (en) * 1973-05-04 1976-10-26 Bayer Aktiengesellschaft Thermoplastic polycarbonate moulding compositions
US3962371A (en) * 1973-12-12 1976-06-08 Bayer Aktiengesellschaft Weather-resistant thermoplasts

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4153646A (en) * 1976-12-11 1979-05-08 Bayer Aktiengesellschaft Graft copolymers
US4161452A (en) * 1977-01-28 1979-07-17 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
US4160739A (en) * 1977-12-05 1979-07-10 Rohm And Haas Company Polyolefinic copolymer additives for lubricants and fuels
US4357445A (en) * 1980-03-07 1982-11-02 Bayer Aktiengesellschaft Process for the production of cross-linked graft copolymers

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SE7601932L (sv) 1976-09-06
GB1517243A (en) 1978-07-12
NL7602269A (nl) 1976-09-07
FR2303032B1 (enrdf_load_stackoverflow) 1979-08-24
JPS51126290A (en) 1976-11-04
BE839124A (fr) 1976-09-03
FR2303032A1 (fr) 1976-10-01
IT1061680B (it) 1983-04-30
CA1088245A (en) 1980-10-21
DE2509403C2 (de) 1983-09-29
DE2509403A1 (de) 1976-09-16

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